CN102560651A - Dielectric crystal sodium borate mandelate dihydrate and its preparation method and application - Google Patents

Abstract

The present invention relates to a kind of new function crystal two that organic/inorganic is compound hydration boric acid mandelic acid sodium salts and its preparation method and application. The chemical formula of the material is C32H28Na2B2O14, and space group is C2 (No.5), and cell parameter is a=16.404 (5) B=8.524 (5) C=24.609 (5)

α=90.00 °, β=105.46 °, γ=90.00 °, Z=4, unit-cell volume V=3316 (2)

Its preparation process are as follows: boric acid, sodium hydroxide and mandelic acid are reacted in water by 1: 1: 2 molar ratio, after saturated solution is made, body block monocrystalline is prepared using aqueous solution cooling method. The crystal all has low dielectric constant, lesser dielectric loss along different crystalline axis directions, it is provided simultaneously with good thermal stability and machinability, has potential application value in terms of the solid-state devices such as electricity resonator, capacitor, filter and surface acoustic wave and integrated optoelectronic device. The present invention is easily operated, and raw material is simple, and without complicated production equipment, manufacturing cost is low, less energy consumption, is suitable for batch production.

Description

A kind of dielectric crystal two hydration boric acid racemic melic acid sodium salts

Technical field

(molecular formula is C to the present invention relates to the novel dielectric crystal two hydration boric acid racemic melic acid sodium salts of a kind of organic/inorganic compound ₃₂H ₂₈Na ₂B ₂O ₁₄) and its production and use, belong to the artificial crystal material field in the technical field of optoelectronic functional materials.

Background technology

Along with developing rapidly of electronic industry equipment and large-scale integrated circuit, widely used electrical condenser begins towards high energy storage, miniaturized and helps directions such as environmental protection to stride forward in the dielectric materials field.Exploitation has unique dielectric properties, and the dielectric materials that has higher mechanical strength and workability simultaneously becomes one of dielectric hot research fields.To being applied in the dielectric materials of electronic applications, except its dielectric properties satisfy the demands, also need the following requirement of material As soon as possible Promising Policy: good calorifics stability and heat conductivity; Suitable physical strength and degree of finish; Be easy to graphical and corrosion, simultaneously can compatible follow-up complex devices work program etc.Up to now, seeking new dielectric materials and the performance of improving existing material, and aspects such as the technology of solution in the following process process is integrated, coupling compatibility also have a lot of work to do.

Current research to dielectric materials mainly concentrates on two aspects, and the one, development has the dielectric materials of high-k, high dielectric strength, existing in this respect a large amount of bibliographical information; The 2nd, exploitation has higher heat resistance, good mechanical and physical strength, low dielectric loss and the type material of ultralow dielectric.As for pottery, the glass etc., often exist the drawback that fragility is big, processing temperature is high, subsequent treatment process is complicated for typical inorganic materials, be difficult to compatibility with the integrated processing technology of the circuit of continuous development; And there is certain inferior position in traditional organic materials at aspects such as calorifics, electricity and mechanical propertys, and its energy storage density was difficult to get a greater increase in short duration.Therefore, the organic/inorganic composite material that has good mechanical properties and dielectric properties concurrently begins to obtain people's extensive concern in this field.

Wherein, the borate cpd of hybrid has caused people's interest, and this mainly is because through molecular designing and regulation and control, this type of material can combine the performance advantage of organic constituent and inorganic component effectively.This compounds also possibly demonstrate novel character except possessing excellent dielectric properties, can realize multi-functional composite shape matl.Involved in the present invention to the molecular formula of two hydration boric acid racemic melic acid sodium salts be C ₃₂H ₂₈Na ₂B ₂O ₁₄, oblique system, spacer is C2.Consider crystal symmetry to the anisotropic influence of dielectric properties, for measuring variant axial specific inductivity, we adopt aqueous solution cooling method to obtain large size single crystal.Result of study to the crystal dielectric properties shows: this crystal has low specific inductivity and less dielectric loss, and good thermostability and workability, has the potential using value in the dielectric field.

Summary of the invention

The objective of the invention is to disclose a kind of organic/inorganic compound new crystal two hydration boric acid racemic melic acid sodium salts, concrete technical scheme is following:

C ₃₂H ₂₈Na ₂B ₂O ₁₄Synthesize in solution and carry out, select racemic melic acid (C ₈H ₈O ₃), boric acid (H ₃BO ₃) and sodium hydroxide (NaOH) as raw material, the mol ratio of three kinds of reactants is 2: 1: 1, adopts water as solvent in the preparation process.Reaction equation is following:

8C ₈H ₈O ₃+4H ₃BO ₃+4NaOH＝2C ₃₂H ₂₈Na ₂B ₂O ₁₄+11H ₂O

With C ₈H ₈O ₃And H ₃BO ₃In water, in solution, slowly add NaOH by the stoichiometric ratio mixed dissolution then, whole process is tangible thermopositive reaction.After question response was complete, evaporating solvent can obtain raw material just.

Adopt aqueous solution cooling method to prepare crystal, concrete experimentation is following:

Utilize the first raw material of method purification of recrystallization, adopt the method for sporadic nucleation to obtain little crystal grain.Material dissolution after the purification is (volume ratio is 1: 1) in water/acetonitrile.Prepare 45 ℃ saturated solution; Bakingout process under 47～48 ℃ temperature slowly is cooled to saturation point then and introduces crystal grain, and rate of temperature fall is made as 0.2 ℃/day; Through about 20 days time, can obtain to have regular exterior appearance, good transparency and high-quality crystal.

We record the crystalline structure of this borate cpd, can be described as 2{Na ⁺[B{O ₂CCH (O) Ph} ₂] ^-2H ₂O.Wherein the end group O atom of each B atom and two racemic melic acid molecules forms B-O key, anionic group [B{O ₂CCH (O) Ph} ₂] ^-With BO ₄Tetrahedron is the main support skeleton; Each Na ⁺With 7 oxygen atom ligands on every side, form a serious distored polyhedron configuration.The concrete structural parameter of this compound are following:

Molecular formula is C ₃₂H ₂₈Na ₂B ₂O ₁₄, its spacer is C2 (No.5), unit cell parameters is a=16.404 (5)

B=8.524 (5)

C=24.609 (5)

α=90.00 °, β=105.46 °, γ=90.00 °, Z=4, unit-cell volume V=3316 (2)

Borate cpd provided by the invention is synthetic in the aqueous solution under the normal temperature condition, and the crystal by adopting aqueous solution cooling method obtains.The method practicality that is adopted is very strong, and the synthesis and preparation process of raw material is fairly simple, productive rate is high, and the method for growing crystal has the strong advantage of universality.

This borate cpd is the novel dielectric crystal material of a kind of organic/inorganic compound.The advantage of this material is that thermostability is higher, and the crystalline color is very shallow, is almost water white transparency, and light absorption effect is very little.Its physical and chemical performance is stable, places and can not decompose in that air is medium-term and long-term, and the dielectric devices that therefore uses this material and designed can be worked in air for a long time.

Description of drawings

Fig. 1 is the C in the embodiment of the invention 2 ₃₂H ₂₈Na ₂B ₂O ₁₄Crystallogram.

Fig. 2 is C among the present invention ₃₂H ₂₈Na ₂B ₂O ₁₄The crystalline structural representation.

Fig. 3 is C among the present invention ₃₂H ₂₈Na ₂B ₂O ₁₄Crystal anionic group [B{O ₂CCH (O) Ph} ₂)] ^-Synoptic diagram.

Embodiment

Below in conjunction with specific embodiment technical scheme of the present invention is further specified.

1. crystalline is synthetic

Embodiment 1:

About C ₃₂H ₂₈Na ₂B ₂O ₁₄Synthesizing of raw material, adopt water as solvent, with C ₈H ₈O ₃, H ₃BO ₃With raw material at the beginning of three kinds of the NaOH be to mix at 2: 1: 1 according to mol ratio, the chemical equation of reaction is following:

8C ₈H ₈O ₃+4H ₃BO ₃+4NaOH＝2C ₃₂H ₂₈Na ₂B ₂O ₁₄+11H ₂O

Its purity of chemical reagent and the manufacturer that use are:

C ₈H ₈O ₃: Aladdin reagent company, analytical pure,

H ₃BO ₃: Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure

NaOH: Chemical Reagent Co., Ltd., Sinopharm Group, analytical pure

Practical implementation step: with 0.02mol C ₈H ₈O ₃With 0.01mol H ₃BO ₃Join in the 20ml deionized water, slowly add 0.01mol NaOH under the intensively stirred situation, continue to stir 30min to the solution achromaticity and clarification.The solution that obtains is carried out millipore filtration, and solvent evaporated promptly obtains raw material.

Embodiment 2:

About C ₃₂H ₂₈Na ₂B ₂O ₁₄The crystalline preparation.

Utilize the method for sporadic nucleation to obtain little crystal grain, adopt aqueous solution cooling method to prepare monocrystalline then, temperature-controlled precision is 0.1 ℃, and crystal growth equipment is for build voluntarily.Concrete operations are: as solvent, both volume ratios are 1: 1 with water/acetonitrile.Take by weighing 0.02mol C ₃₂H ₂₈Na ₂B ₂O ₁₄Be dissolved in the 30ml mixed solvent, be made into 45 ℃ of saturated solutions, introduce behind the crystal grain speed cooling according to 0.2 ℃/day, through after 20 days the C of water white transparency, neat appearance ₃₂H ₂₈Na ₂B ₂O ₁₄Crystal is of a size of 8 * 6 * 3mm ³

Case study on implementation 3:

Of embodiment 1, different is to add C in the raw material building-up process ₈H ₈O ₃, H ₃BO ₃With the mol ratio of NaOH be 2: 1: 1～2, the amount that promptly can add NaOH through regulating is controlled the pH value of solution value.When pH value of solution value scope is between 7～8, obtain identical C ₃₂H ₂₈Na ₂B ₂O ₁₄Compound.

Case study on implementation 4:

Of embodiment 1, different is to adopt yellow soda ash (Na in the raw material building-up process ₂CO ₃) replacement NaOH, reactant C ₈H ₈O ₃, H ₃BO ₃And Na ₂CO ₃Mol ratio be 2: 1: 0.5～1.Can add Na through regulating ₂CO ₃Amount control pH value of solution value, obtain identical C ₃₂H ₂₈Na ₂B ₂O ₁₄Compound.

Case study on implementation 5:

Of embodiment 1, different is to adopt sodium hydrogencarbonate (NaHCO in the raw material building-up process ₃) replacement NaOH, reactant C ₈H ₈O ₃, H ₃BO ₃And NaHCO ₃Mol ratio be 2: 1: 1～2.Can add NaHCO through regulating ₃Amount control pH value of solution value, obtain identical C ₃₂H ₂₈Na ₂B ₂O ₁₄Compound.

The above; It only is preferable case study on implementation of the present invention; Be not that the present invention is done any restriction, every any simple modification that technical spirit is done above case study on implementation according to the present invention, change and equivalence change, and still belong within the present invention program's the protection domain.

2, performance test

We are to C ₃₂H ₂₈Na ₂B ₂O ₁₄The crystalline Dielectric Properties is found: this crystal all has lower specific inductivity and less dielectric loss along different crystalline axis direction, is a kind of novel organic/inorganic compound functional crystal material that the using value of potential is arranged at aspects such as integrated electro solid state devices.。

Claims (5)

1. the new function crystal two hydration boric acid racemic melic acid sodium salts of a hybrid, it is characterized in that: the molecular formula of this compound is C ₃₂H ₂₈Na ₂B ₂O ₁₄, its spacer is C2 (No.5), unit cell parameters is a=16.404 (5)

B=8.524 (5)

C=24.609 (5)

α=90.00 °, β=105.46 °, γ=90.00 °, Z=4, unit-cell volume V=3316 (2)

2. described two hydration boric acid racemic melic acid sodium salt crystalline preparing methods of claim 1 is characterized in that: said compound crystal is synthetic in 40 ℃～50 ℃ the aqueous solution, reactant racemic melic acid C ₈H ₈O ₃, boric acid H ₃BO ₃With sodium hydroxide NaOH as raw material, C ₈H ₈O ₃: H ₃BO ₃: the ratio of the amount of substance of NaOH 2: 1: 1; Solubleness and the solubility coefficient of resultant of reaction in water/acetonitrile equal solvent is bigger, adopts water/acetonitrile as solvent falling temperature method growing crystal.

3. preparation method as claimed in claim 2 is characterized in that: said sodium hydroxide is by yellow soda ash Na ₂CO ₃Replace, can obtain identical C ₃₂H ₂₈Na ₂B ₂O ₁₄Compound.

4. preparation method as claimed in claim 2 is characterized in that: said sodium hydroxide is by sodium hydrogencarbonate NaHCO ₃Replace, can obtain identical C ₃₂H ₂₈Na ₂B ₂O ₁₄Compound.

5. described crystalline material C of claim 1 ₃₂H ₂₈Na ₂B ₂O ₁₄Purposes: this material is having the potential using value aspect the solid unit such as electricity syntonizer, electrical condenser, strainer and surface acoustic wave and integrated optoelectronic device; Method practicality of the present invention is very strong, and preparation cost is low, technology is simple, productive rate is high.

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